EP0214805B1 - Einen Feldeffekttransistor benutzender Fühler und dessen Herstellungsverfahren - Google Patents

Einen Feldeffekttransistor benutzender Fühler und dessen Herstellungsverfahren Download PDF

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Publication number
EP0214805B1
EP0214805B1 EP86306571A EP86306571A EP0214805B1 EP 0214805 B1 EP0214805 B1 EP 0214805B1 EP 86306571 A EP86306571 A EP 86306571A EP 86306571 A EP86306571 A EP 86306571A EP 0214805 B1 EP0214805 B1 EP 0214805B1
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Prior art keywords
gate electrode
groups
sensing material
monomolecular film
hydrophilic polymer
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EP86306571A
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French (fr)
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EP0214805A2 (de
EP0214805A3 (en
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Kazufumi Ogawa
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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Priority claimed from JP60190776A external-priority patent/JPS6250657A/ja
Priority claimed from JP60190772A external-priority patent/JPS6250656A/ja
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Publication of EP0214805A3 publication Critical patent/EP0214805A3/en
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/414—Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
    • G01N27/4145—Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS specially adapted for biomolecules, e.g. gate electrode with immobilised receptors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S438/00—Semiconductor device manufacturing: process
    • Y10S438/939—Langmuir-blodgett film utilization

Definitions

  • This invention is concerned with a sensor comprising a field effect transistor having a gate electrode and a sensing material fixed to the gate electrode.
  • Sensors comprising field effect transistors (FET) are used as pH sensors, sensors of various ions, bio-sensors, and for other purposes.
  • Known bio-sensors typically comprise glass electrodes having proteins or enzymes fixed to their surface or FETs having gate electrodes with proteins or enzymes fixed thereto.
  • the known methods of bonding proteins or enzymes to such surfaces comprise directly applying the protein or enzyme to the surface; or mixing the protein or enzyme with a resin and applying the mixture to the surface; or bonding the protein or enzyme to resin particles which are then applied to the surface; or bonding the protein or resin by means of an organic film.
  • the protein or enzyme tends to become detached during use of the sensor and the durability of the sensor is not adequate.
  • the protein or enzyme becomes partially deactivated so that the sensitivity of the sensor is inadequate.
  • a sensor comprising a field effect transistor having a gate electrode and a sensing material fixed to the gate electrode, characterised in that the gate electrode surface has a reactive monomolecular film or a thin film of a photosensitive hydrophilic polymer directly thereon and the sensing material is bonded to the film by means of Schiffs base or CNBr induced bonding whereby the sensing material retains its activity.
  • a method of making a sensor which comprises forming a field effect transistor having a gate electrode on a semiconductor substrate and fixing a sensing material to the gate electrode, characterised by the steps of:
  • the monomolecular film is formed all over the substrate of said semiconductor surface and is exposed, except that part on the gate electrode area, to an energy beam which deactivates said reactive monomolecular film.
  • a thin film of a photosensitive hydrophilic polymer is formed on said semiconductor substrate;
  • a first embodiment of sensor is made by first forming an FET 12 on a p-type semiconductor substrate 10.
  • the FET 12 is formed in a conventional manner and it comprises n+ type source, drain regions 14, 16, source, drain electrodes 18, 20, gate oxide film 22, gate electrode 24, and insulation film 26.
  • the semiconductor substrate 10 on which the FET 12 is formed is covered with a resist layer 28 and only the resist on gate electrode 24 is exposed, developed and removed to form an opening 30 (Fig. 1).
  • a reactive monomolecular film is then formed through the opening 30 with a compound comprising a straight hydrocarbon chain with a vinyl or acetylene group at one end and a chlorosilane group at the other end (the chlorosilane derivative).
  • the monomolecular film 32 of the chlorosilane derivative is formed by a chemical adsorption process (Fig.2).
  • the metal oxide surface of the gate electrode 24 and the chlorosilane groups of the chlorosilane derivative selectively react with each other to form a monomolecular film of the formula:
  • the film may be formed, for example, by dipping the FET 12 for 2 or 3 minutes into a solution of the chlorosilane derivative in a mixture of 80% n-hexane, 12% carbon tetrachloride and 8% chloroform, the solution containing from 2.0 x 10 ⁇ 3 to 5.0 x 10 ⁇ 2 mol/litre of the chlorosilane derivative.
  • the spatial arrangement of the monomolecular film 32 is shown diagrammatically in Fig. 3; it will be seen that the film is bonded to the metal oxide of the gate electrode 24 by a bond 34 of the formula
  • the vinyl groups 36 of the chlorosilane derivative are arranged in an orderly manner on the free surface of the monomolecular film 32.
  • the resist pattern 28 (Figs. 1 and 2) is then removed and the substrate bearing the monomolecular film 32 is dipped into a 1 mol/litre solution of dibolan in tetrahydrofuran at room temperature and then into an aqueous solution containing 0.1 mol/litre of NaOH and 30% H2O2 in order to add hydroxyl groups 38 to the vinyl groups 36 (or acetylene groups) on the surface of the monomolecular film 32.
  • the substrate is then dipped into an aqueous periodate solution which oxidises the -OH groups to aldehyde groups 40 (Fig. 5) in accordance with equation (1):
  • a protein or enzyme having a desired specific activity is then fixed to the film 32 by the reaction shown in equation (2): where R2-NH2 is a protein or enzyme.
  • Figs. 6 and 7 show the resulting product as diagrammatically in Figs. 6 and 7.
  • Fig. 6 shows the protein or enzyme 42 chemically linked to monomolecular film 32 and
  • Fig. 7 shows the sensor having the protein or enzyme sensing material 44 bonded thereto.
  • the coated substrate is then diced and the appropriate electrodes attached thereto to complete the production of the bio-sensor.
  • LB Langmuir-Blodgett
  • the monomolecular film was formed only on the gate electrode by using the resist 28, but the same effect can be obtained by forming a chlorosilane derivative film 34,36 all over the surface of the substrate (see Fig. 8) and then polymerising the vinyl or acetylene groups in all areas except that of the gate electrode by exposure to an energy beam 46 (which is such as to cause polymerisation of said groups). This has the effect of deactivating the vinyl or acetylene groups in all areas 48 other than the gate electrode area. The vinyl or acetylene groups in the gate electrode are then converted into the carbinol groups as previously described (Fig.4).
  • FIG. 9 A third embodiment of sensor and its method of production are shown in Figs. 9 to 12.
  • a substrate 10 bearing an FET 12 having the same features as that of Fig. 1 is coated with a thin film 50 of a photosensitive hydrophilic polymer.
  • the film 50 is formed by spin coating the substrate with an aqueous solution of the polymer, for example a solution of 10g of pullulan having a molecular weight of 200,000 and 1g of ammonium dichromate in 100cc of water.
  • the film 50 has a thickness of about 0.5 ⁇ m.
  • a photo mask having a desired pattern for example a photomask 54 having an opening 52 corresponding to and aligned with the gate electrode 24, the film is exposed to light 56 (Fig.10) and developed to leave a hydrophilic polymer film pattern 58 selectively on the gate electrode (Fig.11).
  • the coated substrate is then dipped in an aqueous periodate solution to oxidise the surface -OH groups to aldehyde groups in accordance with equation (4):
  • a protein or enzyme having a desired specific activity is then reacted with the CHO group- containing film in accordance with equation (2) above.
  • the coated substrate is then diced and appropriate electrodes are attached thereto to complete the production of the bio-sensor.
  • pullulan instead of pullulan, other polysaccharides such as pectin, proteins such as gelatin or casein, or water-soluble polymers, such as polyvinyl alcohol and polyvinyl pyrrolidone may be used to form the thin film of hydrophilic polymer. Any other film-forming material which contains hydroxyl groups in its molecule, such as novolak resins, can also be used for this purpose.
  • polysaccharides such as pectin, proteins such as gelatin or casein, or water-soluble polymers, such as polyvinyl alcohol and polyvinyl pyrrolidone
  • Any other film-forming material which contains hydroxyl groups in its molecule such as novolak resins, can also be used for this purpose.
  • Pullulan which is partially acetylated (degree of replacement 1.5 to 2.5) can also be used in place of pullulan; in this case the film is formed using acetone as solvent.
  • the photosensitive thin film can also be made using optical cross-linking agents other than ammonium dichromate, such as other dichromates, diazo compounds, such as diazo resin, or diazide compounds, such as 4,4'-diazide-stilbene-2,2'-disulphonic acid sodium salt.
  • optical cross-linking agents other than ammonium dichromate such as other dichromates, diazo compounds, such as diazo resin, or diazide compounds, such as 4,4'-diazide-stilbene-2,2'-disulphonic acid sodium salt.

Claims (14)

  1. Sensor, umfassend einen Feldeffekttransistor mit einer Gateelektrode und einem Sensormaterial, das an die Gateelektrode angebracht ist, dadurch gekennzeichnet, daß die Oberfläche der Gateelektrode einen reaktiven monomolekularen Film oder einen dünnen Film aus einem lichtempfindlichen hydrophilen Polymer direkt daran hat und daß das Sensormaterial an den Film mittels einer durch eine Schiff-Base oder CNBr hervorgerufenen Bindung gebunden ist, wodurch das Sensormaterial seine Aktivität behält.
  2. Sensor nach Anspruch 1, dadurch gekennzeichnet, daß das Sensormaterial ein Protein oder ein Enzym ist.
  3. Sensor nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der reaktive monomolekulare Film aus einer Verbindung gebildet ist, die eine gerade Kohlenwasserstoffkette, die bis zu 25 Kohlenstoffatome enthält, mit einer Vinyl- oder Acetylengruppe an einem Ende und einer Chlorsilangruppe an dem anderen Ende umfaßt.
  4. Sensor nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das lichtempfindliche hydrophile Polymer Hydroxyl- oder Carbonsäuregruppen enthält.
  5. Sensor nach einem der Ansprüche 1, 2 und 4, dadurch gekennzeichnet, daß die Bindung zwischen dem lichtempfindlichen hydrophilen Polymer und einem Sensormaterial, welches ein Protein oder Enzym ist, durch eine Bindung einer der folgenden Formeln bewirkt wird:
    Figure imgb0011
     oder -CH=N-
  6. Sensor nach einem der Ansprüche 1, 2, 4 und 5, dadurch gekennzeichnet, daß das lichtempfindliche hydrophile Polymer von einem Polysaccharid, einem Protein oder einem wasserlöslichen synthetischen Polymer abgeleitet ist.
  7. Sensor nach Anspruch 6, dadurch gekennzeichnet, daß das lichtempfindliche hydrophile Polymer von Pektin, Kasein, Polyvinylalkohol oder Polyvinylpyrrolidon abgeleitet ist.
  8. Sensor nach einem der Ansprüche 1, 2 und 4 bis 7, dadurch gekennzeichnet, daß das hydrophile Polymer durch Vernetzen mit einem optischen Vernetzungsmittel, welches ein Dichromat, eine Diazoverbindung oder eine Diazidverbindung ist, lichtempfindlich gemacht wird.
  9. Sensor nach Anspruch 8, dadurch gekennzeichnet, daß das optische Vernetzungsmittel Ammoniumdichromat, ein Diazoharz oder 4,4'-Diazidstilben-2,2'-disulfonsäure-Natriumsalz ist.
  10. Verfahren zum Herstellen eines Sensors, welches das Bilden eines Feldeffekttransistors mit einer Gateelektrode auf einem Halbleitersubstrat und das Fixieren eines Sensormaterials an der Gateelektrode umfaßt, gekennzeichnet durch die Schritte:
    - Bilden einer Photolackschicht auf dem Halbleitersubstrat außer in dem Bereich der Gateelektrode;
    - Bilden eines reaktiven monomolekularen Films auf der Oberfläche der Gateelektrode, wobei der reaktive monomolekulare Film mittels eines oberflächenaktiven Silan-Mittels, welches eine reaktive Gruppe umfaßt, gebildet ist;
    - Umwandeln der reaktiven Gruppen des oberflächenaktiven Silan-Mittels in Hydroxylgruppen;
    - Umwandeln der Hydroxylgruppen in Aldehydgruppen;
    - Fixieren eines Sensormaterials, welches ein Protein oder Enzym ist, an die Aldehydgruppen mittels einer durch eine Schiff-Base oder CNBr hervorgerufenen Bindung; und
    - Entfernen der Photolackschicht.
  11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß das oberflächenaktive Silan-Mittel eine Verbindung ist, die eine gerade Kohlenwasserstoffkette, die bis zu 25 Kohlenstoffatome enthält, mit einer Vinyl- oder Acetylengruppe an einem Ende und einer Chlorsilangruppe an dem anderen Ende umfaßt, wobei die Chlorsilangruppen mit der Oberfläche der Gateelektrode reagieren und die Vinyl- oder Acetylengruppen in Aldehydgruppen umgewandelt werden.
  12. Verfahren nach Anspruch 10 oder 11, dadurch gekennzeichnet, daß der monomolekulare Film auf der Oberfläche der Gateelektrode durch ein chemisches Adsorptionsverfahren oder durch ein Langmuir-Blodgett-Verfahren gebildet wird.
  13. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß anstelle der Verwendung einer Photolackschicht zum Bilden des monomolekularen Films auf der Gateelektrode, der monomolekulare Film auf dem gesamten Substrat der Halbleiteroberfläche gebildet wird und mit Ausnahme des Teils in dem Gateelektrodenbereich einem Energiestrahl ausgesetzt wird, der den reaktiven monomolekularen Film desaktiviert.
  14. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß anstelle der Bildung eines monomolekularen Films auf der Gateelektrode ein dünner Film aus einem lichtempfindlichen hydrophilen Polymer auf dem Halbleitersubstrat gebildet wird;
    der dünne Film aus einem lichtempfindlichen hydrophilen Polymer von dem Halbleitersubstrat mit Ausnahme des Bereichs auf der Gateelektrode entfernt wird unter Verwendung einer Maske mit einer Öffnung, die der Gateelektrode entspricht;
    die hydrophilen Gruppen des Polymers in Aldehydgruppen umgewandelt werden und letztere mit dem Sensormaterial umgesetzt werden, oder die hydrophilen Gruppen des Polymers mit Cyanobromid und dann mit dem Sensormaterial umgesetzt werden.
EP86306571A 1985-08-29 1986-08-26 Einen Feldeffekttransistor benutzender Fühler und dessen Herstellungsverfahren Expired - Lifetime EP0214805B1 (de)

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JP190776/85 1985-08-29
JP60190776A JPS6250657A (ja) 1985-08-29 1985-08-29 バイオセンサ−およびその製造方法
JP60190772A JPS6250656A (ja) 1985-08-29 1985-08-29 バイオセンサ−およびその製造方法
JP190772/85 1985-08-29

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EP0214805A3 EP0214805A3 (en) 1988-07-06
EP0214805B1 true EP0214805B1 (de) 1993-05-26

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US4881109A (en) 1989-11-14
EP0214805A2 (de) 1987-03-18
EP0214805A3 (en) 1988-07-06
DE3688489D1 (de) 1993-07-01
US4960722A (en) 1990-10-02
DE3688489T2 (de) 1993-09-16

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